Very large cooperative effects in heterobimetallic titanium-chromium catalysts for ethylene polymerization/copolymerization

Shaofeng Liu, Alessandro Motta, Aidan R. Mouat, Massimiliano Delferro, Tobin J Marks

Research output: Contribution to journalArticle

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Abstract

The heterobimetallic complexes, (Ε5-indenyl)[1- Me2Si(tBuN)TiCl2]-3-CnH 2n-[N,N-bis(2-(ethylthio)ethyl)amine]CrCl3 (n = 0, Ti-C0-CrSNS; n = 2, Ti-C2-CrSNS; n = 6, Ti-C6-CrSNS), (Ε5-indenyl)[1- Me2Si(tBuN)TiCl2]-3-C2H 4-[N,N-bis((o-OMe-C6H4)2P)amine] CrCl3 (Ti-C2-CrPNP), and (Ε 5-indenyl)[1-Me2Si(tBuN)TiCl 2]-3-C2H4-[N,N-bis((diethylamine)ethyl)-amine] CrCl3 (Ti-C2-CrNNN), are synthesized, fully characterized, and employed as olefin polymerization catalysts. With ethylene as the feed and MAO as cocatalyst/activator, SNS-based complexes Ti-C 0-CrSNS, Ti-C2-CrSNS, and Ti-C 6-CrSNS afford linear low-density polyethylenes (LLDPEs) with exclusive n-butyl branches (6.8-25.8 branches/1000 C), while under identical polymerization conditions Ti-C2-CrPNP and Ti-C2-CrNNN produce polyethylenes with heterogeneous branching (C2, C4, and C≥ 6) or negligible branching, respectively. Under identical ethylene polymerization conditions, Ti-C0-CrSNS produces polyethylenes with higher activity (4.5× and 6.1×, respectively), Mn (1.3× and 1.8×, respectively), and branch density (1.4× and 3.8×, respectively), than Ti-C2-CrSNS and Ti-C 6-CrSNS. Versus a CGCEtTi + SNSCr tandem catalyst, Ti-C0-CrSNS yields polyethylene with somewhat lower activity, but with 22.6× higher Mn and 4.0× greater branching density under identical conditions. In ethylene +1-pentene competition experiments, Ti-C0-CrSNS yields 5.5% n-propyl branches and 94.5% n-butyl branches at [1-pentene] = 0.1 M, and the estimated effective local concentration of 1-hexene is ∼8.6 M. In contrast, the tandem CGCEtTi + SNSCr system yields 91.0% n-propyl branches under identical reaction conditions. The homopolymerization and 1-pentene competition results argue that close Ti···Cr spatial proximity together with weak C-H···Ti and C-H···S interactions significantly influence relative 1-hexene enchainment and chain transfer rates, supported by DFT computation, and that such effects are conversion insensitive but cocatalyst and solvent sensitive.

Original languageEnglish
Pages (from-to)10460-10469
Number of pages10
JournalJournal of the American Chemical Society
Volume136
Issue number29
DOIs
Publication statusPublished - Jul 23 2014

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Polyethylenes
Chromium
Titanium
Polymerization
Copolymerization
Amines
Ethylene
Polyethylene
Catalysts
Linear low density polyethylenes
Monoamine Oxidase
Alkenes
Homopolymerization
Discrete Fourier transforms
Olefins
1-pentene
ethylene
Experiments
1-hexene

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Very large cooperative effects in heterobimetallic titanium-chromium catalysts for ethylene polymerization/copolymerization. / Liu, Shaofeng; Motta, Alessandro; Mouat, Aidan R.; Delferro, Massimiliano; Marks, Tobin J.

In: Journal of the American Chemical Society, Vol. 136, No. 29, 23.07.2014, p. 10460-10469.

Research output: Contribution to journalArticle

Liu, Shaofeng ; Motta, Alessandro ; Mouat, Aidan R. ; Delferro, Massimiliano ; Marks, Tobin J. / Very large cooperative effects in heterobimetallic titanium-chromium catalysts for ethylene polymerization/copolymerization. In: Journal of the American Chemical Society. 2014 ; Vol. 136, No. 29. pp. 10460-10469.
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abstract = "The heterobimetallic complexes, ({\^I}•5-indenyl)[1- Me2Si(tBuN)TiCl2]-3-CnH 2n-[N,N-bis(2-(ethylthio)ethyl)amine]CrCl3 (n = 0, Ti-C0-CrSNS; n = 2, Ti-C2-CrSNS; n = 6, Ti-C6-CrSNS), ({\^I}•5-indenyl)[1- Me2Si(tBuN)TiCl2]-3-C2H 4-[N,N-bis((o-OMe-C6H4)2P)amine] CrCl3 (Ti-C2-CrPNP), and ({\^I}• 5-indenyl)[1-Me2Si(tBuN)TiCl 2]-3-C2H4-[N,N-bis((diethylamine)ethyl)-amine] CrCl3 (Ti-C2-CrNNN), are synthesized, fully characterized, and employed as olefin polymerization catalysts. With ethylene as the feed and MAO as cocatalyst/activator, SNS-based complexes Ti-C 0-CrSNS, Ti-C2-CrSNS, and Ti-C 6-CrSNS afford linear low-density polyethylenes (LLDPEs) with exclusive n-butyl branches (6.8-25.8 branches/1000 C), while under identical polymerization conditions Ti-C2-CrPNP and Ti-C2-CrNNN produce polyethylenes with heterogeneous branching (C2, C4, and C{\^a}‰¥ 6) or negligible branching, respectively. Under identical ethylene polymerization conditions, Ti-C0-CrSNS produces polyethylenes with higher activity (4.5× and 6.1×, respectively), Mn (1.3× and 1.8×, respectively), and branch density (1.4× and 3.8×, respectively), than Ti-C2-CrSNS and Ti-C 6-CrSNS. Versus a CGCEtTi + SNSCr tandem catalyst, Ti-C0-CrSNS yields polyethylene with somewhat lower activity, but with 22.6× higher Mn and 4.0× greater branching density under identical conditions. In ethylene +1-pentene competition experiments, Ti-C0-CrSNS yields 5.5{\%} n-propyl branches and 94.5{\%} n-butyl branches at [1-pentene] = 0.1 M, and the estimated effective local concentration of 1-hexene is ∼8.6 M. In contrast, the tandem CGCEtTi + SNSCr system yields 91.0{\%} n-propyl branches under identical reaction conditions. The homopolymerization and 1-pentene competition results argue that close Ti···Cr spatial proximity together with weak C-H···Ti and C-H···S interactions significantly influence relative 1-hexene enchainment and chain transfer rates, supported by DFT computation, and that such effects are conversion insensitive but cocatalyst and solvent sensitive.",
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T1 - Very large cooperative effects in heterobimetallic titanium-chromium catalysts for ethylene polymerization/copolymerization

AU - Liu, Shaofeng

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AU - Delferro, Massimiliano

AU - Marks, Tobin J

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N2 - The heterobimetallic complexes, (Ε5-indenyl)[1- Me2Si(tBuN)TiCl2]-3-CnH 2n-[N,N-bis(2-(ethylthio)ethyl)amine]CrCl3 (n = 0, Ti-C0-CrSNS; n = 2, Ti-C2-CrSNS; n = 6, Ti-C6-CrSNS), (Ε5-indenyl)[1- Me2Si(tBuN)TiCl2]-3-C2H 4-[N,N-bis((o-OMe-C6H4)2P)amine] CrCl3 (Ti-C2-CrPNP), and (Ε 5-indenyl)[1-Me2Si(tBuN)TiCl 2]-3-C2H4-[N,N-bis((diethylamine)ethyl)-amine] CrCl3 (Ti-C2-CrNNN), are synthesized, fully characterized, and employed as olefin polymerization catalysts. With ethylene as the feed and MAO as cocatalyst/activator, SNS-based complexes Ti-C 0-CrSNS, Ti-C2-CrSNS, and Ti-C 6-CrSNS afford linear low-density polyethylenes (LLDPEs) with exclusive n-butyl branches (6.8-25.8 branches/1000 C), while under identical polymerization conditions Ti-C2-CrPNP and Ti-C2-CrNNN produce polyethylenes with heterogeneous branching (C2, C4, and C≥ 6) or negligible branching, respectively. Under identical ethylene polymerization conditions, Ti-C0-CrSNS produces polyethylenes with higher activity (4.5× and 6.1×, respectively), Mn (1.3× and 1.8×, respectively), and branch density (1.4× and 3.8×, respectively), than Ti-C2-CrSNS and Ti-C 6-CrSNS. Versus a CGCEtTi + SNSCr tandem catalyst, Ti-C0-CrSNS yields polyethylene with somewhat lower activity, but with 22.6× higher Mn and 4.0× greater branching density under identical conditions. In ethylene +1-pentene competition experiments, Ti-C0-CrSNS yields 5.5% n-propyl branches and 94.5% n-butyl branches at [1-pentene] = 0.1 M, and the estimated effective local concentration of 1-hexene is ∼8.6 M. In contrast, the tandem CGCEtTi + SNSCr system yields 91.0% n-propyl branches under identical reaction conditions. The homopolymerization and 1-pentene competition results argue that close Ti···Cr spatial proximity together with weak C-H···Ti and C-H···S interactions significantly influence relative 1-hexene enchainment and chain transfer rates, supported by DFT computation, and that such effects are conversion insensitive but cocatalyst and solvent sensitive.

AB - The heterobimetallic complexes, (Ε5-indenyl)[1- Me2Si(tBuN)TiCl2]-3-CnH 2n-[N,N-bis(2-(ethylthio)ethyl)amine]CrCl3 (n = 0, Ti-C0-CrSNS; n = 2, Ti-C2-CrSNS; n = 6, Ti-C6-CrSNS), (Ε5-indenyl)[1- Me2Si(tBuN)TiCl2]-3-C2H 4-[N,N-bis((o-OMe-C6H4)2P)amine] CrCl3 (Ti-C2-CrPNP), and (Ε 5-indenyl)[1-Me2Si(tBuN)TiCl 2]-3-C2H4-[N,N-bis((diethylamine)ethyl)-amine] CrCl3 (Ti-C2-CrNNN), are synthesized, fully characterized, and employed as olefin polymerization catalysts. With ethylene as the feed and MAO as cocatalyst/activator, SNS-based complexes Ti-C 0-CrSNS, Ti-C2-CrSNS, and Ti-C 6-CrSNS afford linear low-density polyethylenes (LLDPEs) with exclusive n-butyl branches (6.8-25.8 branches/1000 C), while under identical polymerization conditions Ti-C2-CrPNP and Ti-C2-CrNNN produce polyethylenes with heterogeneous branching (C2, C4, and C≥ 6) or negligible branching, respectively. Under identical ethylene polymerization conditions, Ti-C0-CrSNS produces polyethylenes with higher activity (4.5× and 6.1×, respectively), Mn (1.3× and 1.8×, respectively), and branch density (1.4× and 3.8×, respectively), than Ti-C2-CrSNS and Ti-C 6-CrSNS. Versus a CGCEtTi + SNSCr tandem catalyst, Ti-C0-CrSNS yields polyethylene with somewhat lower activity, but with 22.6× higher Mn and 4.0× greater branching density under identical conditions. In ethylene +1-pentene competition experiments, Ti-C0-CrSNS yields 5.5% n-propyl branches and 94.5% n-butyl branches at [1-pentene] = 0.1 M, and the estimated effective local concentration of 1-hexene is ∼8.6 M. In contrast, the tandem CGCEtTi + SNSCr system yields 91.0% n-propyl branches under identical reaction conditions. The homopolymerization and 1-pentene competition results argue that close Ti···Cr spatial proximity together with weak C-H···Ti and C-H···S interactions significantly influence relative 1-hexene enchainment and chain transfer rates, supported by DFT computation, and that such effects are conversion insensitive but cocatalyst and solvent sensitive.

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